Treatment of raw materials containing titanium

ABSTRACT

Production of titanium dioxide which is characterized by recovery of reusable H 2  SO 4 , highly pure Fe oxide and hydroxide and fractional recovery of Mn, V and Cr, etc., from FeSO 4 . nH 2  O and waste acid of 20 - 40% H 2  SO 4  containing abundant heavy metallic ions, which are by-produced in the production of TiO 2  by dissolution of Ti raw materials such as ilmenite, steel production slag, such as electric furnace slag, convertor slag with H 2  SO 4 .

BACKGROUND OF THE INVENTION

This invention is concerned with the production of titanium dioxide which is characterized by recovery of reusable H₂ SO₄, high pure Fe oxide and hydroxide and fractional recovery of Mn, V and Cr, etc., from FeSO₄.nH₂ O and waste acid of 20 - 40% H₂ SO₄ containing abundant heavy metallic ions, which are by-products of the production of TiO₂ by dissolution of Ti raw materials, such as, ilmenite, steel production slag, such as, electric furnace slag, convertor slag with H₂ SO₄.

In the conventional production of TiO₂ using H₂ SO₄, the required amount of 98% H₂ SO₄ per 1 ton of TiO₂ product is 3.5 to 4.2 tons. Nevertheless, an economical treatment of FeSO₄.nH₂ O and waste acids produced in abundance as by-products after the separation of Ti compounds by the hydrolysis process has not been found and the practice of retaining or discarding them in the untreated form has given rise to serious pollution problems. This invention has been developed to overcome the faults of the conventional production process described above.

SUMMARY OF THE INVENTION

The present invention relates to the production of titanium dioxide which is characterized by the recovery of reusable H₂ SO₄, high pure Fe oxide and hydroxide and fractional recovery of Mn, V and Cr, etc., from FeSO₄.nH₂ O and waste acid of 20 - 40% H₂ SO₄ containing abundant heavy metallic ions, which are by-products in the production of TiO₂ by dissolution of Ti raw materials, such as, ilmenite, steel production slag, such as electric furnace slag, convertor slag, with H₂ SO₄.

The summary of this invention is as follows. The present invention is firstly characterized by the absence of the production of waste acids and FeSO₄.nH₂ O is as follows: The aqueous solution pretreated after dissolution of the Ti raw materials with H₂ SO₄ is brought into contact and mixed with an organic solvent (A) to extract metallic ions, such as, Cr³⁺ and Nb⁵⁺ ions in the first stage and the bulk of Ti ions in the resulting aqueous solution is separated by well-known hydrolysis process in the 2nd stage. The metallic ions, such as, Ti, Mn and V ions remaining in the resulting aqueous solution are extracted into an organic solvent (B) in the 3rd stage, an organic solvent (C) extracts Fe ions in the resulting aqueous solution after the oxidation of Fe²⁺ ions to Fe³⁺ ions in the 4th stage and V⁵⁺ ions in the resulting aqueous solution are extracted into an organic solvent (D) in the 5th stage. The resulting aqueous solution from the 5th stage is the reusable regenerated acid for use in dissolution of raw materials.

The second characteristic of the present invention is concerned with the extraction of Fe ions from the aqueous solution using Cl₂ gas for the oxidation as follows: After the conversion of Fe²⁺ ions in the aqueous solution from the 3rd stage as described hereinafter to Fe³⁺ ions using Cl₂ gas, the amount of HCl required to extract Fe³⁺ ions in the aqueous solution as the Fe chloride complex is added to the resulting aqueous solution and is contacted with an organic solvent (E) to extract Fe-Cl ions into the organic phase.

The third characteristic of this invention is concerned with the reduction of energy in the concentration process of the acid as follows. FeSO₄.nH₂ O which is a by-product in the pretreatment process is dissolved with water or acids from the fourth stage, the oxidation of Fe²⁺ ions in the resulting aqueous solution to Fe³⁺ ions is finished and then Fe³⁺ ions in the resulting aqueous solution are extracted into the organic phase by contact of the organic solvent (C). The resulting increase in the concentration of regenerated acid by several repetitions of the above operation as necessary produces reduction in the energy required in the following concentration processes of the acid.

The fourth characteristic of the present invention is concerned with the treatment of FeSO₄.nH₂ O with the fractional extraction of Mn and Fe ions as follows. After dissolution of the FeSO₄.nH₂ O by-product with water, Mn²⁺ ions in the resulting aqueous solution are extracted with an organic solvent (F) into the organic phase to separate them from the Fe²⁺ ions in the resulting aqueous solution, the Fe²⁺ ions are oxidized to Fe³⁺ ions and then the Fe³⁺ ions are extracted into the organic phase by contacting them with the organic solvent (C). The concentration of the recovered acid is enhanced by several repetitions of the above operation as necessary and by recycling for dissolution of the raw materials by way of the concentration process.

The fifth characteristic of this invention is concerned with the reduction of the recovery cost by increasing the Fe concentration in the aqueous solution which is introduced into the recovery process of HCl and Fe as follows. The Fe concentration of the aqueous solution introduced into the recovery process of HCl and Fe is increased by extracting Fe³⁺ ions in the back-extraction solution of the organic solvent (C) with contact of the organic solvent (E) and stripping with water. The increased Fe concentration produces the reduction of recovery cost.

The 6th characteristic of this invention is concerned with the reasonable recovery of Fe compounds using both solvent extraction and diaphragm-electrolysis techniques as follows. The back-extraction solution of the organic solvent (C) or of the organic solvent (E) is introduced into the cathode compartment of the diaphragm-electrolysis, Fe³⁺ ions are reduced to Fe²⁺ ions there, free acid is transferred to the anode compartment and hydrated Fe oxide or hydroxide is recovered by the contact of air or oxygen with the aqueous solution in the cathode compartment containing a lesser amount of free recovered acid.

The 7th characteristic of this invention is concerned with the fractional recovery of metallic ions coextracted into the organic solvent (B) as follows. Mn, V and Fe ions coextracted into the organic solvent (B) are scrubbed with HCl or H₂ SO₄, Ti ions in the organic solvent (B) is back-extracted into the aqueous solution with contact of (NH₄)₂ CO₃ + NH₃ solution, and then the organic solvent converted from H type to NH₃ type in the above operation is again converted to H type with contact of H₂ SO₄. When Cr³⁺ ions are coextracted, those in the organic phase can be recovered into the aqueous solution with contact of HCl + H₂ O₂ or HCl + NaCl solution. Thus, the individual metallic ion coextracted into the organic solvent (B) are fractionally recovered. When Al³⁺ and Mg²⁺ ions are accumulated in the recovered acid during recycle of the recovered acid, the enhancement of their ions concentration is depressed by taking one part of out the extraction system and the solution is taken out is recovered as (NH₄)₂ SO₄ by neutralizing with NH₃.

Since the desired purpose can be accomplished by installation of the process based on this invention along with the conventional production process of TiO₂, the control of production line of TiO₂ and its quality are unchangeable and consequently the practical application of this invention is very easy and the economical recovery of valuable metals which could not be economically recovered hitherto becomes possible. Therefore, the present invention has a great deal of industrial values for the connected industrial fields.

DETAILED EXPLANATION OF THE INVENTION

The present invention will be explained in detail with reference to drawings.

FIG. 1 and FIG. 2 show a general flow-sheet of the present invention.

FIG. 3 is a graph showing Nb extraction equilibrium curve with amine in the first stage.

FIG. 4 is a graph showing Cr³⁺ ion extraction equilibrium curve with amine in the first stage.

FIG. 5 is a graph showing Cr³⁺ ion back-extraction equilibrium curve with HCl or H₂ SO₄ in the first stage.

FIG. 6 is a graph showing Cr³⁺ ion extraction equilibrium curve from sulfate solution in the third stage.

FIG. 7 is a graph showing Ti⁴⁺ ion extraction equilibrium curve in the third stage.

FIG. 8 is a graph showing Ti⁴⁺ ion back-extraction equilibrium curve in the third stage.

FIG. 9 is a graph showing Cr³⁺ ion back-extraction equilibrium curve in the third stage.

FIG. 10 is a graph showing Fe³⁺ ion extraction equilibrium curve with D2EHPA in the fourth stage.

FIG. 11 is a graph showing HFeCl₄ extraction equilibrium curve with TBP in the fourth stage.

FIG. 12 is a graph showing FeCl₄ ⁻ extraction equilibrium curve with amine in the fourth stage.

FIG. 13 is a graph showing Fe³⁺ ion back-extraction equilibrium curve in the fourth stage.

FIG. 14 is a graph showing HFeCl₄ and FeCl₄ ⁻ back-extraction equilibrium curve in the fourth stage.

FIG. 15 is a graph showing V⁵⁺ ion extraction equilibrium curve in the fifth stage.

FIG. 16 is a graph showing the relation between V⁵⁺ ion extraction and pH.

FIG. 17 is a graph showing V⁵⁺ ion back-extraction equilibrium curve in the fifth stage.

FIG. 18 is a graph showing the relation between H₂ SO₄ concentration and Fe³⁺ ion extraction coefficient.

FIG. 19 is a graph showing the relation between Mn²⁺ and Fe²⁺ ions extraction coefficient and pH.

FIG. 20 is a graph showing Fe²⁺ ion scrub equilibrium curve.

The following explanation is based on the experiments carried out by the inventors. The typical chemical analysis of ilmenite used commonly as a raw material of TiO₂ is shown as follows.

    ______________________________________                                         TiO.sub.2                                                                             FeO     Fe.sub.2 O.sub.3                                                                       V.sub.2 O.sub.5                                                                      MnO   Cr.sub.2 O.sub.3                                                                     MgO                                   ______________________________________                                         54.20  26.60   14.20   0.16  0.40  0.07  1.03                                  53.13  19.11   22.95   0.19  0.94  0.03  0.92                                                       Values in wt.%                                            ______________________________________                                    

2 to 2.5 tons of raw material described above per 1 ton of TiO₂ product is sulfatized with 3.5 to 4 tons of 98% H₂ SO₄. After heating to sulfatize, Fe³⁺ ions in the resulting aqueous solution is completely reduced with Fe scrap. The clarified solution is produced by removing undissolved residues. The chemical composition of the aqueous solution which is obtained after removing one part of Fe ions as FeSO₄.nH₂ O crystal is shown as follows

    ______________________________________                                         TiO.sub.2                                                                             Fe.sup.2+                                                                              T . H.sub.2 SO.sub.4                                                                     Cr.sup.3+                                                                            Mn.sup.2+                                                                            V.sup.4+                                                                            Mg.sup.2+                            ______________________________________                                         200    32      300       0.1   1.8   0.3  1.6                                                       Values in g/l                                             ______________________________________                                    

The synthesized solution having the above mentioned chemical composition and no Fe³⁺ ions was as a standard solution in the following experiment.

(1) The First Stage

The extraction of Cr³⁺ and Nb⁵⁺ ions with the organic solvent (A) is run before hydrolysis process owing to their superior extractability in lower concentrations of free acid and higher temperatures of the aqueous solution. Organic solvent (A) is made up of primary, amine secondary, tertiary or quaternary amines, for example, "Primene JMT" (tradename, primary amine produced by Rohm and Haas), "Amberlite LA-1" (tradename, secondary amine produced by Rohm and Haas), "Alamine 336" (tradename, tertiary amine produced by General Mills), and "Aliquat 336" (tradename, quaternary amine produced by General Mills), 2 - 5% higher alcohols such as, octanol, dodecanol or isodecanol as a modifier and aromatic aliphatic or paraffin hydrocarbon as a diluent. The organic solvents used in this experiment indicate only one example and of course similar organic solvents can be utilized.

- Extraction -

The extraction test is done with the increased concentration of Cr³⁺ and Nb⁵⁺ ions by adding and adjusting the Cr₂ (SO₄)₃ and NbCl₅ concentration in the aqueous solution described above. Cr³⁺ and Nb⁵⁺ ions are extracted according to the following formulas.

    __________________________________________________________________________     NbO(SO.sub.4).sub.2.sup.-                                                             + H.sub.2 RN                                                                         + H.sup.+                                                                           ⃡                                                                    (H.sub.2 RNH.sup.+) . NbO(SO.sub.4).sub.2.sup.-                                             (see FIG. 3)                                  (Aq)     (Org) (Aq) (Org)                                                      CrSO.sub.4                                                                            + H.sub.2 RN                                                                         + H.sup.+                                                                           ⃡                                                                    (H.sub.2 RNH.sup.+) . CrSO.sub.4.sup.-                                                      (see FIG. 4)                                  (Aq)     (Org) (Aq) (Org)                                                      __________________________________________________________________________

The extractability of Cr³⁺ ions by amines follows the order: primary amine > secondary amine > tertiary amine. However, there is little difference in the extractability of Nb⁵⁺ ions with various amines. The main factors of the Cr³⁺ ions extraction are temperature, contact time and concentration of free acid. The high extractability of Cr³⁺ ions is obtained the 50° to 80° C and the longer contact time the higher the concentration of free acid.

- Stripping -

Cr³⁺ ions extracted into the organic solvent (A) are stripped from the organic phase with by contact with HCl or H₂ SO₄ according to the under formula.

    __________________________________________________________________________     (H.sub.2 RNH.sup.+) . CrSO.sub.4.sup.-                                                     + 1/2 H.sub.2 SO.sub.4                                                                ⃡                                                                    H.sub.2 RN                                                                         + 1/2 Cr.sub.2 (SO.sub.4).sub.3                                                         + 2 H.sup.+                                  (Org)         (Aq)   (Org) (Aq)     (Aq)                                       Back-extraction test (see FIG. 5)                                                     Temp.                                                                             Back-extraction %                                                                         Temp.                                                                               Back-extraction %                                    __________________________________________________________________________     15% HCl                                                                              20° C                                                                       88.9% 20% H.sub.2 SO.sub.4                                                               20° C                                                                         81.4%                                                20% HCL                                                                              20° C                                                                       99.0% 30% H.sub.2 SO.sub.4                                                               60° C                                                                         98.0%                                                __________________________________________________________________________

After removing Cr³⁺ ions from the organic solvent (A), Nb⁵⁺ ions is stripped from the organic phase with contact of NH₄ F + NH₃ solution according to the following formula.

    __________________________________________________________________________     (H.sub.2 RNH.sup.+)                                                                  .                                                                               NbO(SO.sub.4).sub.2.sup.-                                                             + NH.sub.4 F                                                                         + 4NH.sub.4 OH                                                                        ⃡                                                                    H.sub.2 RN                                                                         + Nb(OH).sub.5                                                                        + 2(NH.sub.4).sub.2 SO.sub.4                                                            + NH.sub.4 F                  (Org)           (Aq)  (Aq)   (Org) (ppt)  (Aq)     (Aq)                        __________________________________________________________________________

(2) The Second Stage

A large amount of Ti ions is removed as Ti hydroxide by hydrolysis process of the resulting aqueous solution from which Cr³⁺ and Nb⁵⁺ ions have been extracted. The approximate chemical composition of the liquor after separation of titanium is shown as follows.

    ______________________________________                                         TiO.sub.2                                                                            Fe.sup.2+                                                                             T . H.sub.2 SO.sub.4                                                                      Cr.sup.3+                                                                            V.sup.4+                                                                             Mn.sup.2+                                                                             Mg.sup.2+                           ______________________________________                                         7     32     300        Tr    0.3   2.8    1.6                                                   Values in g/l                                                ______________________________________                                    

(3) The Third Stage

Ti ions and one part of the V⁴⁺ ions in the resulting aqueous solution are extracted into the organic phase with the organic solvent (B). When there are Cr³⁺ ions from the omission of the first stage, Cr³⁺ ions are coextracted with Ti ions into the organic solvent (B) as shown in FIG. 6. The organic solvent (B) is composed of alkyl phosphoric acid, for example, D2EHPA(Di-2-ethyl hexyl phosphoric acid) and H₂ DDP (Mono-dodecyl phosphoric acid), 2 - 5% higher alcohols, such as, octanol, decanol or isodecanol as a modifier and aromatic, aliphatic or paraffin hydrocarbons as a diluent.

- Extraction -

Ti⁴⁺ ions are extracted with the organic solvent (B) according to the under formula.

    __________________________________________________________________________     Ti.sup.4+                                                                         + 4 [(RO).sub.2 POOH]                                                                     ⃡                                                                    Ti[(RO).sub.2 POO].sub.4                                                                + 4 H.sup.+                                                                         (see FIG. 7)                                     (Aq) (Org)      (Org)      (Aq)                                                __________________________________________________________________________

The resulting solution includes a small amount of V⁵⁺ ions and they are slightly extracted. While, Fe³⁺ ions are not commonly contained in the resulting solution, but if Fe³⁺ ions exist in it, they are completely extracted like Ti⁴⁺ ions. Mn²⁺ ions are extracted as the concentration of free acid lowers.

- Continuous extraction test -

The liquor as shown in the following table was continuously treated with the organic solvent (B) at a flow rate of 0.15 l/min. using a mixer-settler (100 mm W × 500 mm L × 180 mm H). The mixer was of the pump-suction type and rotated at 120 - 310 r.p.m. depending on the interface level in the settler using a non-stepwise speed changer. The organic solvent used consists of 20% D2EHPA, 3% octanol and kerosene in balance.

    ______________________________________                                         The third stage - Extraction                                                   Flow                                                                           ratio     Inlet(Aq)      Outlet(Aq)                                            Appa- O/A     Ti    V   Fe   H.sub.2 SO.sub.4                                                                     Ti  V    Fe   H.sub.2 SO.sub.4              ratus                                                                          5 Stage                                                                              1.0/    7.1   0.2 31.8 300   tr  0.18 31.8 300                           mixer-                                                                         settler                                                                              1.0                                                                      ______________________________________                                         Outlet (Org)        Solvent                                                    ______________________________________                                         Ti     V      Fe      H.sub.2 SO.sub.4                                                                       20%D2EHPA                                        7.1    0.02   <0.01   <0.1    3% octanol diluted                                                             with kerosene                                    ______________________________________                                          Values in g/l                                                            

- Scrubbing -

V⁴⁺, Fe³⁺ and Mn²⁺ ions, which are extracted in the low concentration of free acid, coextracted with Ti⁴⁺ ions into the organic solvent (B) are scrubbed from the organic solvent (B) by contact with of HCl, H₂ SO₄ or HNO₃, but Ti⁴⁺ and Cr³⁺ ions are not scrubbed.

    ______________________________________                                         Scrubbing test with 15% HCl                                                    Metallic ions                                                                             Flow                                                                concentration                                                                             ratio              shaking                                                                              Back-                                      in the org. phase                                                                         O/A     Temp.      time  extraction %                               ______________________________________                                         Mn.sup.2+                                                                             0.2 g/l 1.0      Room temp.                                                                             15 min.                                                                              99.5%                                    V.sup.4+                                                                              0.5 g/l 1.0     "        "     99.0%                                    Fe.sup.3+                                                                             1.0 g/l "       "        "     98.5%                                    Cr.sup.3+                                                                             0.5 g/l "       60° C                                                                            30 min.                                                                              0%                                       Ti.sup.4+                                                                             7.0 g/l "       Room temp.                                                                              "     0%                                       ______________________________________                                    

The organic solvent (B) extracted Ti ions are scrubbed by contact of HCl, H₂ SO₄ or HNO₃ to remove V⁴⁺ and Mn²⁺ ions, etc. coextracted with Ti⁴⁺ ions into the organic solvent (B). The selection of HCl, H₂ SO₄ or HNO₃ as a scrub solution is done after consideration of the finished recovery form of scrubbed V and Mn, etc. The organic solvent (B) after the scrubbing process includes only Ti⁴⁺ ions, but includes also Cr³⁺ ions provided that the first stage is omitted.

- Continuous scrubbing test -

The apparatus for the test is the same one used for the extraction process and the flow rates of organic aqueous phases are 0.5 l/min. and 0.05 l/min., respectively.

    ______________________________________                                         The third stage - Scrubbing                                                          Flow              Outlet  Outlet                                         Appa- ratio   Inlet (Org)                                                                              (Org)   (Aq)                                           ratus O/A     Ti     V    Ti   V    Ti  V   Note                               ______________________________________                                         5 Stage                                     Temp.: 35° C                mixer-                                                                               10/1    7.10   0.02 7.10 0.01 --  0.2 Scrub sol.                         settler                                     : 15% HCl                          ______________________________________                                          Values in g/l                                                            

- Stripping -

Ti⁴⁺ ions in the organic solvent (B) after the scrubbing process are stripped in the following stripping process.

Back-extraction test of Ti ions with various back-extraction solutions

Flow ratio : 0/A = 1/1, Shaking time: 15 min. Temp.: Room temp.

    ______________________________________                                         Back-                          Back-ex-                                        extraction %                   traction %                                      ______________________________________                                         6N H.sub.2 SO.sub.4                                                                    0          0.5 N HF        64.71                                       12N H.sub.2 SO.sub.4                                                                   0          0.5N NH.sub.4 F 75.03                                       6N HCl  0          6N H.sub.2 SO.sub.4 +1% H.sub.2 O.sub.2                                                        36.04                                       12N HCl 0          (NH.sub.4).sub.2 SO.sub.4                                                                      0                                           4N HNO.sub.3                                                                           0          (NH.sub.4).sub.2 SO.sub.4 + NH.sub.3                                                           98.0                                        8N HNO.sub.3                                                                           0.4        Saturated (NH.sub.4).sub.2 CO.sub.3                                                            99.5                                        11N H.sub.3 PO.sub.4                                                                   5.7        1M (NH.sub.4).sub.2 CO.sub.3 + NH.sub.3                                                        99.5                                        ______________________________________                                    

It is considered from the result of the back-extraction test that 0.5 M - saturated (NH₄)₂ CO₃ + NH₃ solutions with pH values maintained between 7 and 9.5 and over 2 M(NH₄)₂ SO₄ + NH₃ solutions with pH values maintained over 7.0 are the most suitable back-extraction solutions of Ti ions from the standpoint of cost and subsequent operations. Therefore, the mechanism of the back-extraction of Ti ions is shown as follows.

    __________________________________________________________________________     Ti [(RO).sub.2 POO].sub.4                                                                +  2 (NH.sub.4).sub.2 CO.sub.3                                                            +  4 NH.sub.4 OH                                                                         ⃡                                                                     Ti(OH).sub.4 +                               (Org)        (Aq)       (Aq)      (ppt)                                        4 [(RO).sub.2 POONH.sub.4 ]                                                               +  2 (NH.sub.4).sub.2 CO.sub.3                                                            (see FIG. 8)                                             (Org)         (Aq)                                                             __________________________________________________________________________

As shown in the above formula, (NH₄)₂ CO₃ used for the back-extraction forms HCO₃ ⁻ ion in the back-extraction of Ti and HCO₃ ⁻ ion formed reacts with NH₃ to form (NH₄)₂ CO₃ again.

    ______________________________________                                         The third stage - Stripping                                                            Flow    Inlet   Outlet                                                                               Outlet                                                   ratio   (Org    (Org) (Aq)                                             Apparatus                                                                              O/A     Ti      Ti    Ti    Note                                       ______________________________________                                         5 Stage-                            1M(NH.sub.4).sub.2 CO.sub.3                mixer-  1/1     7.10    0.01  7.10* + NH.sub.3                                 settler                             pH: 9.5                                                                        Temp.: 23° C                        ______________________________________                                          Remark : The value of Ti* in the back-extraction solution is one obtained      the remelting the precipitate as Ti(OH).sub.4.                           

As the organic solvent (B) becomes the NH₄ type by stripping Ti ions, it is converted to the H type by with contact of H₂ SO₄ or HCl in the following process. When Cr³⁺ ions are coextracted, Cr³⁺ ions are stripped by contact with of H₂ SO₄ + H₂ O₂, HCl + H₂ O₂ or HCl + NaCl solution and then the NH₄ type of the organic solvent (B) is converted to the H type. (see FIG. 9).

(4) The Fourth Stage

- Extraction -

Fe²⁺ ions in the resulting solution in which Ti ions are separated are converted to Fe³⁺ ions with H₂ O₂, oxygen, high pressure air or electro-oxidation and Fe³⁺ ions in the resulting aqueous solution are extracted into the organic phase with the organic solvent (C). The organic solvent (C) is composed of alkyl phosphoric acid, for example, D2EHPA, mixed solvent of alkyl phosphoric acid and LIX-63 (tradename, chelate reagent produced by General Mills) or α-bromo lauric acid, 2 - 5% higher alcohol as a modifier and aromatic, aliphatic or paraffin hydrocarbon as a diluent.

The extraction mechanism of Fe³⁺ ion with alkyl phosphoric acid is shown as follows. (See FIG. 10)

    ______________________________________                                         Fe.sup.3+                                                                           +     3 [(RO).sub.2 POOH]                                                                         =    Fe [(RO).sub.2 POO].sub.3                                                                 +   3 H.sup.+                          (Aq)       (Org)             (Org)          (Aq)                               ______________________________________                                    

While, Fe²⁺ ions are oxidized to Fe³⁺ ions using Cl₂ gas and Fe ions are extracted into the organic phase with the organic solvent (E) after adding HCl to the resulting aqueous solution in an amount enough to extract the Fe³⁺ ions as an Fe chloride complex. The organic solvent (E) is made up of phosphoric acid ester, for example, TBP (tri-butyl phosphoric acid), TOP (tri-octyl phosphoric acid), DBBP (di-butyl butyl phosphonate) or TOPO (tri-octyl phosphine oxide) and aromatic, aliphatic or paraffin hydrocarbons as a diluent. Moreover, the organic solvent (E) may be made up of primary, secondary, tertiary or quaternary amine, higher alcohol as a modifier and aromatic, aliphatic, or paraffin hydrocarbons as a diluent. The test used Primene-JMT as a primary amine, LA-1 as a secondary amine, Alamine 336 as a tertiary amine and Aliquat 336 as a quaternary amine. Of course, similar amines can be utilized besides the amines described above. Furthermore, mixed solvent of phosphoric acid ester, such as, TBP and tertiary amine such as TOA (tri-octyl amine) can be used. Fe ions are extracted into the organic phase with phosphoric acid ester or amine according to the following formulas.

    __________________________________________________________________________     FeCl.sub.3                                                                         + H.sup.+                                                                          + Cl.sup.-                                                                          + 2TBP                                                                               ⃡                                                                    HFeCl.sub.4 . 2TBP                                                                     (Extraction by TBP                                                             see FIG. 12)                                      (Aq)  (Aq)                                                                               (Aq) (org) (Org)                                                     FeCl.sub.4.sup.-                                                                   + (R.sub.3 NH).sup.+                                                                  ⃡                                                                    (R.sub.3 NH).sup.+ . FeCl.sub.4.sup.-                                                   (Extraction                                                                    by tertiary                                              (Aq)  (Org)  (Org)    amine. see FIG. 12)                                      __________________________________________________________________________

- Stripping -

Fe³⁺ ions extracted into the organic phase with the organic solvent (C) are stripped from the organic phase with HCl and the organic solvent (C) is regenerated as shown in the following formula.

    __________________________________________________________________________     Fe[(RO).sub.2 POO].sub.3                                                                + 3HCl                                                                               ⃡                                                                    FeCl.sub.3                                                                         + 3[(RO).sub.2 POOH]                                                                      (see FIG. 13)                                  (Org)      (Aq)  (Aq)  (Org)                                                   __________________________________________________________________________

While, Fe chloride complex extracted into the organic phase with the organic solvent (E) is stripped from the organic phase with water and the organic solvent (E) is regenerated according to the following formulas (see FIG. 14).

    ______________________________________                                         HFeCl.sub.4 . 2TBP                                                                        +     H.sub.2 O                                                                             ⃡                                                                      FeCl.sub.3                                                                           +   HCl  +   TBP                             (Org)            (Aq)       (Aq)      (Aq)     (Org)                           (R.sub.3 NH.sup.+). FeC1.sub.4.sup.-                                                      +     H.sub.2 O                                                                             ⃡                                                                      FeCl.sub.3                                                                           +   HCl  +   R.sub.3 N                       (Org)            (Aq)       (Aq)      (Aq)     (Org)                           ______________________________________                                    

- Continuous extraction and stripping test -

The apparatus used for the test is the same one used in the first stage. The flow rate of organic and aqueous phases were 0.1 l/min.

    __________________________________________________________________________     Extraction                                                                     Appara-                                                                              Flow ratio                                                                            Inlet(Aq)                                                                              Outlet(Aq)                                                                             Outlet(Org)                                       tus   O/A    Fe  H.sub.2 SO.sub.4                                                                   Fe  H.sub.2 SO.sub.4                                                                   Fe  H.sub.2 SO.sub.4                                                                   Note                                      __________________________________________________________________________     10 Stage                             30% D2EHPA                                mixer-                                                                               3/1    31.8                                                                               300 <0.01                                                                              300 10.6                                                                               <0.01                                                                              3% decanol                                settler                              kerosene                                  15 Stage                                                                       mixer-                                                                               4/1    31.8                                                                               300 <0.01                                                                              300 7.94                                                                               <0.01                                                                              15% TBP                                   settler                              kerosene                                  __________________________________________________________________________      values in g/l  -                                                         

    Stripping                                                                      Appara-                                                                              Flow ratio                                                                            Inlet(Org)                                                                             Outlet(Org)                                                                            Outlet(Aq)                                        tus   O/A    Fe  HCl Fe  HCl Fe  HCl Note                                      __________________________________________________________________________     10 Stage                                                                       mixer                                                                          settler                                                                              1.5/1.0                                                                               10.6                                                                               --  0.1 --  15.9                                                                               150 Room temp.                                                                     150 g/l HCl                                "    10/1   7.94                                                                               20.5                                                                               0.6 1.5 73.4                                                                               189 60° C                                                                   H.sub.2 O                                 __________________________________________________________________________       Values in g/l                                                           

(5) The Fifth Stage

- Extraction -

The resulting aqueous solution extracted off Fe³⁺ ions contains a small amount of Al³⁺, Mg²⁺, Mn²⁺ and V⁴⁺ ions and is reused for dissolution of Ti raw materials through the concentration process. However, since these metallic ions are gradually accumulated in the recycling process, it is necessary to take them out the system and to prevent their accumulation. When acid is taken out the system or is recycled to reuse, it is connected with the improved economization of the apparatus to extract and recover the V⁴⁺ ions which have an economical value among them.

In the case of recycling for reuse, VO(SO₄)₂ ⁻ ions in the resulting aqueous solution which has no Fe ions and 300 - 500 g/l of free acid are extracted into the organic phase by contact of the organic solvent (D). (see FIG. 15). In the other case of taking acid out the system, VO₃ ⁻ ions in the aqueous solution, whose pH values are maintained between 2 and 4 with NH₃, are extracted into the organic phase with contact of the organic solvent (D). FIG. 16 shows the relation between the pH and V extraction coefficient.

The organic solvent (D) is made up of primary, secondary, tertiary or quaternary amine, 2 - 5% higher alcohols such as, octanol, decanol or isodecanol as a modifier and aromatic, aliphatic or paraffin hydrocarbons as a diluent. The amines used for the test are Primene-JMT as a primary amine, LA-1 as a secondary amine, Alamine 381 (tri isooctylamine produced by Ashland Chemical Co.) as a tertiary amine and Aliquat 336 as a quaternary amine. Of course, various similar amines can be commonly utilized besides the amines mentioned above.

- Stripping -

VO(SO₄)₂ ⁻ ions extracted into the organic solvent (D) are stripped from the organic phase with the contact of (NH₄)₂ SO₄. While, VO₃ ⁻ ions extracted into the organic solvent (D) can be stripped with NH₄ Cl + NH₃ (see FIG. 17). Both types of V ions are recovered as the form of NH₄ VO₃.

(6) The Treatment of By-product FeSO₄.nH₂ O

The H₂ SO₄ concentration produced after the extraction of Fe³⁺ ions and almost all heavy metallic ions in the fourth stage is 250 - 300 g/l and consequently this low concentration of H₂ SO₄ enhances the energy cost of the concentration to reuse for the dissolution of raw materials, through the concentration process. The H₂ SO₄ concentration is increased by dissolving FeSO₄.nH₂ O by-produced in the pretreatment process into the aqueous solution from which the Fe³⁺ ions are removed in order to reduce this energy cost. The several repetitions of the above operation in accordance with the demand can diminish the energy cost of concentration. The relation between the H₂ SO₄ concentration and the Fe³⁺ ions extraction coefficient is shown in FIG. 18.

FeSO₄.nH₂ O often includes MnSO₄. As shown in the flow-sheet of FIG. 2, Mn²⁺ ions are separated from Fe²⁺ ions by extracting Mn²⁺ ions by contact of the organic solvent (F) in the lower concentration of free acid produced by the dissolution of the FeSO₄.nH₂ O crystals with water (see FIG. 19).

The organic solvent (F) is composed of alkyl phosphoric acid, for example, D2EHPA, H₂ DDP, 2 - 5% higher alcohol as a modifier and aromatic, aliphatic or paraffin hydrocarbons as a diluent. While, the organic solvent (F) may be made up of mixed solvent of D2EHPA and LIX-63 or primary, secondary, tertiary or quaternary amine. As described above, the mixed solvents consisted of mainly alkyl phosphoric acid and 5 - 20% of LIX-63, aliphatic hydroxy oxime or α-bromo lauric acid are used to extract Mn ions.

A small amount of Fe²⁺ ions coextracted with Mn²⁺ ions are scrubbed from the organic solvent (F) with contact of MnSO₄ solution having 2 - 3.5 of pH values, the organic solvent (F) contains only Mn ions and consequently Mn²⁺ ions are stripped from the organic solvent (F) with 300 g of H₂ SO₄ in the following process.

- Continuous extraction test -

The continuous extraction test using the under-tabulated FeSO₄.nH₂ O by-produced by the H₂ SO₄ process was done and MnSO₄ was added to the resulting solution in order to facilitate the confirmation of the Mn extraction.

    ______________________________________                                         Chemical analysis of FeSO.sub.4 . nH.sub.2 O                                   FeO            TiO.sub.2                                                                              MnO                                                     ______________________________________                                         24.96%         0.22%   0.06%                                                   ______________________________________                                    

The pH value in dissolving 250 g of the above crystal with 1 liter of water was 1.8 and the chemical composition of the resulting solution to which Mn was added was shown as follows.

    __________________________________________________________________________               Total H.sub.2 SO.sub.4                                                                   Fe    Mn    Ti    (Values in g/l)                                    90.7      48.8  2.0   0.3                                            __________________________________________________________________________     Extraction                                                                     Flow ratio   Inlet(Aq)   Outlet(Aq)  Outlet(Org)                               Apparatus                                                                            0/A    Fe  Mn  Ti  Fe  Mn  Ti  Fe  Mn  Ti  Note                          10 Stage                                                                             4/1    48.8                                                                               2.0 0.3 48.4                                                                               0.1 Tr  0.1 0.49                                                                               0.1 20%                           mixer-                                           D2EHPA                        settler                                                                         "    2/1    48.8                                                                               2.0 0.3 48.6                                                                               0.1 Tr  Tr  1.0 0.15                                                                               10% LIX                                                                        63+10%                                                                         D2EHPA                        __________________________________________________________________________      Values in g/l                                                            

Fe²⁺ ions are coextracted with Mn²⁺ ions from pH values between 3.5 and 3.8. In this case, Fe²⁺ ions extracted into the organic phase are scrubbed from the organic solvent (F) with MnSO₄ solution having a pH value of 2 - 2.5 and the concentraton of Mn in the MnSO₄ solution depends on the concentration of the organic solvent (F). (see FIG. 20)

    __________________________________________________________________________     Stripping                                                                      Flow ratio   Inlet(Org)  Outlet(Org) (Outlet(Aq)                               Apparatus                                                                            O/A    Fe  Mn  Ti  Fe  Mn  Ti  Fe  Mn  Ti                                __________________________________________________________________________     5 Stage                                                                              10/1   0.1 0.49                                                                               0.1 --  0.06                                                                               0.6 --  4.8 --  300g/l                        mixer-                                           H.sub.2 SO.sub.4              settler                                                                         "    10/1   Tr  1.0 0.15                                                                               --  0.01                                                                               0.15                                                                               --  9.9 --                                __________________________________________________________________________      Values in g/l                                                            

Ti ions in the organic solvent (F) are not stripped and the organic solvent (F) is recycled. Since the Ti concentration gradually increases, one part of the organic solvent (F) is taken out the system and Ti ions in it are stripped from the organic phase with contact of the (NH₄)₂ CO₃ + NH₄ OH solution.

(7) The Recovery of HCl by Diaphragm -- Electrolysis

As the concentration of Fe³⁺ ions in the back-extraction solution of the organic solvent (C) including Fe³⁺ ions is impossible to be increased as shown in FIG. 13, the introduction of the above back-extraction solution into the apparatus of the recovery by the thermal-decomposition process enhances the energy cost of the recovery and consequently the back-extraction solution is introduced into the cathode compartment of diaphragm-electrolysis, and free HCl produced there by the reduction of FeCl₃ to FeCl₂ is transferred to the anode compartment and recovered.

- Continuous electrolysis test -

The back-extraction solution of the organic solvent (C) is fed into the cathode compartment by a quantitative pump and the aqueous solution of low HCl concentration, which is the back-extraction solution of the organic solvent (C) and contains no Fe ions, is fed into the anode compartment.

    ______________________________________                                         Electrolysis condition                                                         Material of diaphragm :                                                                           Film of Tetra-fluo ethylene                                 Thickness of diaphragm :                                                                          0.103 mm                                                    Void percent diaphragm :                                                                          55 %                                                        Hole diameter diaphragm :                                                                         0.3μ                                                     Water permeability :                                                                              0.48 ml/cm.sup.2 H                                           diaphragm                                                                     Electric resistance :                                                                             0.1 Ω-cm.sup.2                                        Anode : carbon   Cathode :                                                                        Ti (Pt plating)                                             Volume of anode or cathode room :                                                                 5l                                                          Temperature : 24 - 55° C                                                Current density : 2 A/dm.sup.2                                                 ______________________________________                                         - Continuous test at steady state -                                                       Cathode room                                                                               Anode room                                                               Inlet    Outlet Inlet  Outlet                                 ______________________________________                                         Fe.sup.3+                                                                             (g/l)     18.0     0.4    0      --                                     Fe.sup.2+                                                                             (g/l)     --       21.0   0      --                                     HCl    (g/l)     176      27.4   50     178.0                                  Liquor                                                                         volume (1/H)     5.0      4.3    5.0    5.7                                    ______________________________________                                    

The following diaphragms besides the one described above were used.

    __________________________________________________________________________     Material Electric resistance                                                                      Hole dia.                                                                            Void %                                                                               Water permeab.                                  __________________________________________________________________________     Acetic cellose                                                                          0.05 - 0.19Ω-cm.sup.2                                                              0.1 - 0.4μ                                                                        58 - 62%                                                                             0.11-0.3 ml/cm.sup.2                            Polypropylene                                                                           0.12 - 0.27Ω-cm.sup.2                                                              0.2 - 0.4"                                                                           38 - 45%                                                                             0.02-0.2 ml/cm.sup.2                            Ion exchange                                                                   cm.sup.2 1.7 - 3.2 Ψ                                                                          Water content : 38%                                         membrane                                                                       __________________________________________________________________________

The back-extraction solution of the organic solvent (E) is the concentrated solution containing 75 - 85 g/l of Fe and 200 - 240 g/l of HCl as described above. However, it is considered that the energy cost of free HCl recovery by reduction of Fe²⁺ ions in the electrolysis process becomes lower than that by thermal-decomposition process because free HCl exists in the back-extraction solution of the organic solvent (E). As for the ion exchange membrane, any ion exchange membrane may be used.

The solution containing Fe²⁺ ions, which consists of the solution of Fe²⁺ ions produced by electro-reduction of Fe³⁺ ions (FeCl₃ → FeCl₂ + Cl) and the solution which is recovered by transferring the solution, containing abundant HCl unused in the back-extraction, into the anode compartment are converted to FeCl₃ by the oxidation with air or oxygen and one part of the Fe ions is precipitated and separated as hydrated Fe oxide or hydroxide according to the following formula.

    2 FeCl.sub.2 + O + H.sub.2 O = FeCl.sub.3 + HCl + FeO(OH)

Both HCl and FeCl₃ produced in the above formula are introduced again into the cathode compartment of the electrolysis process and HCl and Cl⁻ which are transferred to the anode compartment are recovered by reduction of Fe³⁺ ions to Fe²⁺ ions. When there is the apparatus of thermal-decomposition, Fe₂ O₃ and HCl can be obtained by thermal-decomposition of the concentrated solution produced through several electrolysis processes from the viewpoint of water-balance.

Both Fe₂ O₃ and FeO(OH) obtained as mentioned above are high purity and can be utilized for ferrite and pigment without further purification.

The production of TiO₂ based on this invention has the following advantages.

(1) The adoption of this production method has the extreme advantages in the anti-pollution and economical cost by working out the problem of FeSO₄.nH₂ O -- treatment which has been the most troublesome process.

(2) The recovery of valuable metals, such, as V, Nb and Mn, etc., contained in a small amount is possible by regenerating and reusing the waste acid economically, including a large amount of heavy metal ions in 20 - 40% H₂ SO₄ after the hydrolysis process. The product of the individual valuable metal is recovered in high purity.

(3) The metals such as, Cr whose existence in the raw materials is undesirable can be fractionally recovered with solvent extraction techniques from the aqueous solution before the hydrolysis process and consequently the selection of the raw materials is very easy.

(4) The product-purity of the hydrated Fe oxide and hydroxide by-produced in the acid recovery process is very high as used not only pig iron -- raw materials, but also for valuable ferrite or pigment and consequently the economical value is enhanced.

(5) The whole system is built up as a closed-circuit and the protection of the environment is possible because the great part of the used reagent is recovered or used as a product. 

What is claimed is:
 1. In a method for obtaining titanium dioxide from titanium-containing raw materials wherein the materials are dissolved in sulfuric acid to form an aqueous solution of sulfuric acid containing dissolved titanium and other metals selected from the group consisting of iron, V, Mn, Cr, and Nb, and then forming a precipitate of FeSO₄ .nH₂ O and the titanium in the solution is isolated and subsequently recovered as titanium dioxide from the aqueous solution, the improvement which comprises:1. extracting Cr³⁺ and Nb⁵⁺ ions from the aqueous solution by contacting the aqueous solution with a first organic solvent selected from the group consisting of primary, secondary, tertiary and quaternary amines;
 2. separating the aqueous solution resulting from step (1) and separating a major portion of the titanium ion in the solution by hydrolysis;
 3. separating the aqueous solution resulting from the hydrolysis treatment of step (2) and extracting the titanium ions remaining in the aqueous solution with a second organic solvent selected from the group consisting of alkyl phosphoric acids mixed with from 2 to 5 percent higher alcohols and aromatic, aliphatic or paraffinic hydrocarbons as a diluent;
 4. separating the aqueous solution resulting from the extraction of step (3), oxidizing the Fe⁺² ions therein to Fe⁺³ ions and then extracting the Fe⁺³ ions with a third organic solvent selected from the group consisting of alkyl phosphoric acids in combination with from 2 to 5 percent higher alcohols and aromatic, aliphatic or paraffinic hydrocarbons as a diluent;
 5. separating the aqueous solution resulting from step (4) and extracting the vanadium ions and other remaining heavy metal ions with a fourth organic solvent selected from the group consisting of primary, secondary, tertiary or quaternary amines in combination with from 2 to 5 percent higher alcohols and aromatic, aliphatic or paraffinic hydrocarbons as a diluent; and then
 6. recovering, regenerating and concentrating the sulfuric acid remaining in the aqueous solution resulting from step (5).
 2. The process of claim 1 wherein the second organic solvent after the extraction in step 3 is scrubbed with an aqueous solution of H₂ SO₄, HNO₃ or HCl whereby the Mn, V and Fe ions contained therein are removed, and then the thus treated second organic solvent is back-extracted with an aqueous solution containing (NH₄)₂ CO₃, (NH₄)SO₄, NH₄ F or a combination of NH₄ NO₃ and NH₃ to transfer the Ti⁺⁴ ions into the aqueous solution and then separating the remaining third solvent and then contacting said separated third solvent with H₂ SO₄ and extracting any Cr³⁺ ions in the thus treated solvent by washing with an aqueous solution of HCl and H₂ O₂ or HCl and NaCl.
 3. The process of claim 2 therein the FeSO₄.nH₂ O is dissolved in the aqueous solution from step 3 prior to the extraction with the third solvent.
 4. The process of claim 3 wherein after dissolution of the FeSO₄.nH₂ O in aqueous solution from step 3, Mn²⁺ ions in the resulting solution are extracted with a sixth organic solvent leaving the Fe⁺² ions in the aqueous solution from said extraction for the oxidation treatment.
 5. The process of claim 4 wherein the Fe⁺³ ions in the third solvent are extracted by contacting said third solvent with said sixth solvent and then stripping said sixth solvent with water.
 6. The process of claim 4 wherein a solvent selected from the group consisting of the third extracting solvent, the sixth extracting solvent and combinations thereof, said solvents containing said Fe³⁺ ions, is introduced into the cathode compartment of a diaphragm-electrolysis unit and subjected to electrolysis therein whereby the Fe⁺³ ions are reduced to Fe⁺² and free acid is transferred to the anode compartment and hydrated Fe oxide or hydroxide is recovered by contacting the aqueous solution in the cathode compartment with air or oxygen.
 7. In a method for obtaining titanium dioxide from titanium-containing raw materials wherein the materials are dissolved in sulfuric acid to form an aqueous solution of sulfuric acid containing dissolved titanium and other metals selected from the group consisting of iron, V, Mn, Cr, and Nb, and then forming a precipitate of FeSO₄.nH₂ O and the titanium in the solution is isolated and subsequently recovered as titanium dioxide from the aqueous solution, the improvement which comprises:1. extracting Cr³⁺ and Nb⁵⁺ ions from the aqueous solution by contacting the aqueous solution with a first organic solvent selected from the group consisting of primary, secondary, tertiary and quaternary amines;
 2. separating the aqueous solution resulting from step
 1. and separating a major portion of the titanium ion in the solution by hydrolysis;
 3. separating the aqueous solution resulting from the hydrolysis treatment of step
 2. and extracting the titanium ions remaining in the aqueous solution with a second organic solvent selected from the group consisting of alkyl phosphoric acids mixed with from 2 to 5 percent higher alcohols and aromatic, aliphatic or paraffinic hydrocarbons as a diluent;
 4. separating the aqueous solution resulting from the extracting of step 3., oxidizing the Fe⁺² ions therein to Fe⁺³ ions, adding HCl to the resulting solution to form an iron chloride complex and then extracting the complex from the solution with a fifth organic solvent suitable for dissolving and extracting said complex;5. separating the aqueous solution resulting from step
 4. and extracting the vanadium and other remaining heavy metal ions with a fourth organic solvent selected from the group consisting of primary, secondary, tertiary, or quaternary amines, in combination with from 2 to 5 percent higher alcohols and aromatic, aliphatic or paraffinic hydrocarbons as a diluent; and then
 6. recovering, regenerating and concentrating the sulfuric acid remaining in the aqueous solution resulting from step
 5. 